Bio-based synthetic fluids

ABSTRACT

A method is provided involving altering the viscosity of bio-derived paraffins to produce a paraffinic fluid, where the altering step includes chlorinating the bio-derived paraffins; the bio-derived paraffins include a hydrodeoxygenated product produced by hydrodeoxygenating a bio-based feed where the bio-based feed includes bio-derived fatty acids, fatty acid esters, or a combination thereof; the bio-derived paraffins include n-paraffins; and the n-paraffins have a biodegradability of at least 40% after about 23 days of exposure to microorganisms. Also provided are methods of protecting and/or cleaning a substance by applying the paraffinic fluid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/598,966, filed on Jan. 16, 2015, which is a divisional of U.S.application Ser. No. 13/871,972, filed on Apr. 26, 2013, now U.S. Pat.No. 8,969,259, which claims the benefit of priority from U.S.Provisional Application No. 61/809,183, filed on Apr. 5, 2013, each ofwhich is incorporated herein by reference in its entirety for any andall purposes.

FIELD

The technology relates to production of synthetic fluids frombio-derived feeds. More particularly, this technology relates to methodsfor conversion of animal fat, vegetable oils, and other sources ofbio-based fatty acid/esters into paraffinic fluids suitable for use assolvents, industrial process fluids, and lubricating base oils.

BACKGROUND

Low aromatic hydrocarbon fluids, i.e. typically containing less than 1wt % total aromatics, are used in a diverse range of applications wherechemical inertness, thermal/oxidative stability, low toxicity, and lowodor are desired. These hydrocarbons are characterized by theirparaffinic nature, a carbon number distribution in the C₅-C₄₀ range,preferably in the C₁₅-C₄₀ range. For most applications, the preferredfluids have a flash point greater than about 100° C. Other propertiesspecified for hydrocarbon fluids include viscosity (specification rangedictated by application), and pour point (typically <−10° C.). Mineraloil is an example of a low aromatic hydrocarbon fluid.

As a result of a number of industry trends, such as increased demand fordrilling and hydraulic fracturing fluids and tightening environmentalstandards concerning eco-toxicity, biodegradability, and work placesafety/health, demand for such paraffinic fluids has experienced rapidgrowth. This has coincided with an increased demand for middledistillate fuels (C₁₀-C₂₀ hydrocarbons) that compete for much of thesame petroleum molecules. Furthermore, with high aromatic feeds such astar sands finding their way into the North American petroleum pool, moreextensive upgrading (such as aromatic hydrogenation) is required inorder to meet fluid product specifications. Use of mineral oils incosmetics and food preparation is banned in the European Union due toconcerns about presence of trace amounts of carcinogenic polyaromatichydrocarbons—thus providing the need for synthetic products that areinherently free of these aromatic components.

Synthetic hydrocarbon products have been used for some industrial fluidapplications. For example C₁₆/C₁₅ linear alpha olefins (LAOS) fromoligomerization of ethylene, are used as drilling base fluids. However,this synthetic route is non-selective, producing a wide distribution ofeven carbon number LAOS, mostly in the C₄ to C₁₀ range, such thatfurther expensive processing and separation steps are required toachieve the desired LAO product. Moreover, these even carbon number LAOsin the C₄ to C₁₀ range are chemical intermediates and not end-productssuitable for use in industrial fluid applications.

Use of the Fischer-Tropsch process for producing synthetic hydrocarbonssuitable for certain hydrocarbon fluid applications has also beenreported. However, the FT process is very capital intensive and most ofthe FT manufacturing is dedicated to fuel production. Because thehydrocarbon range of interest for synthetic hydrocarbon fluids comprisesa small percentage of the wide distribution of FT hydrocarbons(C1-C50+), it is more economical to hydrocrack and hydrotreat the FT waxand light oil fractions into complex compositions for fuel use.

There is thus a need for new processes for producing hydrocarbon fluidsfrom alternative feeds. More specifically, there is a need forhydrocarbon fluid products that, based on their feedstocks andconversion processes, are substantially free of aromatics withoutfurther processing such as by aromatic hydrogenation conditions.

SUMMARY

In an aspect, a method is provided involving altering the viscosity ofbio-derived paraffins to produce a paraffinic fluid, where the alteringstep includes oligomerizing bio-derived paraffins, unsaturatingbio-derived paraffins, chlorinating bio-derived paraffins, or acombination of any two or more thereof; the bio-derived paraffins areproduced by hydrodeoxygenating a bio-based feed; the bio-based feedcomprises bio-derived fatty acids, fatty acid esters, or a combinationthereof the bio-derived paraffins comprise n-paraffins; and then-paraffins have a kinematic viscosity of less than about 10 cSt at 40°C. and have a biodegradability of at least 40% after about 23 days ofexposure to microorganisms.

In some embodiments, oligomerizing bio-derived paraffins includescontacting the bio-derived paraffins with an organic peroxide to producean oligomerized product, where the oligomerized product has a kinematicviscosity of at least about 10 cSt at 40° C. In some embodiments, theoligomerized product has a biodegradability of at least about 40% afterabout 23 days of exposure to microorganisms. In some embodiments, theoligomerized product is a dimer, trimer, tetramer, or a mixture of anytwo or more thereof. In some embodiments, the organic peroxide ispresent in an amount between about 2 wt % and about 40 wt % based on thetotal weight of paraffins and organic peroxide. In some embodiments, theorganic peroxide comprises di-tert butyl peroxide (DTBP), 2,5-dimethyl2,5-di(t-butylperoxy)hexane, dicumyl peroxide, dibenzoyl peroxide,dipropyl peroxide, ethyl propyl peroxide, or tert-butyl tert-amylperoxide. In some embodiments, the contacting is performed at atemperature between about 50° C. and about 250° C. In some embodiments,the oligomerized product is used as a drilling fluid, a hydraulicfracturing fluid, a metal working fluid, a protecting agent, or acombination of any two or more thereof.

In some embodiments, chlorinating the bio-derived paraffins includescontacting the bio-derived paraffins with chlorine gas at a temperaturebetween about 60° C. and about 150° C. to produce a chlorinated product,where the chlorinated product comprises haloalkanes; and the chlorinatedproduct has a kinematic viscosity of greater than about 10 cSt at 40° C.In some embodiments, the chlorinated product is used as a protectingagent, a cleaning agent, or a combination of both. In some embodiments,the chlorinated product acts as a flame retardant. In some embodiments,the chlorinated product is used to clean fabric, metal, or plastic.

In some embodiments, unsaturating the bio-derived paraffins comprisesdehydrogenation of the bio-derived paraffins by contacting thebio-derived paraffins with a dehydrogenation catalyst at a temperaturefrom about 360° C. to about 660° C. to produce an olefinic fluid, wherethe olefinic fluid comprises at least about 10 wt % internal olefins inthe C₁₅ to C₁₈ range; and the olefinic fluids have a kinematic viscosityof less than about 10 cSt at 40° C. In some embodiments, the olefinicfluid comprises at least about 20 wt % internal olefins in the C₁₅ toC₁₈ range. In some embodiments, the method further involvesoligomerizing the olefinic fluid to produce dimers, trimers, tetramers,or a mixture of any two or more thereof. In some embodiments, theolefinic fluid is used as a hydraulic fracturing fluid, as a drillingfluid, or a combination of the two.

In some embodiments, the bio-derived paraffins are produced byhydrodeoxygenating the bio-based feed to produce a hydrodeoxygenatedproduct; and at least partially hydroisomerizing the hydrodeoxygenatedproduct to produce a hydroisomerized product; where the bio-derivedparaffins comprise the hydrodeoxygenated product and the hydroisomerizedproduct; the hydrodeoxygenated product comprises n-paraffins; thehydroisomerized product comprises isoparaffins where at least about 80wt % of the isoparaffins are mono-methyl branched paraffins; themono-methyl branched paraffins comprise less than about 30 wt % terminalbranched isoparaffins; and the isoparaffins have a kinematic viscosityof less than about 10 cSt at 40° C. and have a biodegradability of atleast about 40% after about 23 days of exposure to microorganisms. Insome embodiments, the hydrodeoxygenated product includes n-paraffins inthe range of about 80 wt % to about 100 wt %; cycloparaffins in therange of about 1 wt % to about 10 wt %; and less than about 1 wt % totalaromatics.

In some embodiments, the bio-derived fatty acids, fatty acid esters, ora combination thereof comprises algae oils, beef tallow, camelina oil,canola oil, rapeseed oil, castor oil, choice white grease, coconut oil,coffee bean oil, corn oil, cottonseed oil, fish oils, hemp oil, Jatrophaoil, linseed oil, mustard oil, palm oil, palm kernel oil, poultry fat,soybean oil, sunflower oil, tall oil, tall oil fatty acid, Tung oil,used cooking oils, yellow grease, products of the food industry, orcombinations of any two or more thereof. In some embodiments, thebio-derived fatty acids, fatty acid esters, or a combination thereofcomprise soybean oil, corn oil, cottonseed oil, canola oil, coconut oil,sunflower oil, palm oil, palm kernel oil, rapeseed oil, or a combinationof any two or more thereof.

In an aspect, a method is provided involving producing an orifice in asubstrate by at least injecting a viscosity-altered paraffinic fluidinto the substrate, wherein the paraffinic fluid includes ahydrodeoxygenated product and a hydroisomerized product; thehydrodeoxygenated product is produced by hydrodeoxygenating abio-derived feed; the hydroisomerized product is produced by at leastpartially hydroisomerizing the hydrodeoxygenated product; thebio-derived feed includes bio-derived fatty acids, fatty acid esters, ora combination thereof; the hydrodeoxygenated product includesn-paraffins; the hydroisomerized product includes isoparaffins; theparaffinic fluid contains less than about 1 wt % aromatics; and then-paraffins have a kinematic viscosity of less than about 10 cSt at 40°C. and have a biodegradability of at least about 40% after about 23 daysof exposure to microorganisms; the isoparaffins are at least about 80 wt% mono-methyl branched paraffins where the mono-methyl branchedparaffins comprise less than about 30 wt % terminal branchedisoparaffins, have a kinematic viscosity of less than about 10 cSt at40° C., and have a biodegradability of at least about 40% after about 23days of exposure to microorganisms. In some embodiments, the substrateincludes a soil substrate, a topsoil substrate, a subsoil substrate, aclay substrate, a sand substrate, a rock substrate, or a stonesubstrate. In some embodiments, the step of producing an orificeincludes hydraulic fracturing of the substrate with the paraffinicfluid.

In another aspect, a method is provided involving protecting a substanceby applying a paraffinic fluid. In the method, the paraffinic fluidincludes a hydrodeoxygenated product; where the hydrodeoxygenatedproduct is produced by hydrodeoxygenating a bio-derived feed; thebio-derived feed comprises bio-derived fatty acids, fatty acid esters,or a combination thereof; the hydrodeoxygenated product comprisesn-paraffins; the paraffinic fluid contains less than 1 wt % aromatics;and the n-paraffins have a kinematic viscosity of less than about 10 cStat 40° C. and have a biodegradability of at least 40% after about 23days of exposure to microorganisms. In some embodiments, thehydrodeoxygenated product includes n-paraffins in the range of about 80wt % to about 100 wt %; cycloparaffins in the range of about 1 wt % toabout 10 wt %; less than about 1 wt % total aromatics. In someembodiments, the paraffinic fluid further comprises a hydroisomerizedproduct produced by at least partially hydroisomerizing thehydrodeoxygenated product; where the hydroisomerized product comprisesisoparaffins where at least about 80 wt % of the isoparaffins aremono-methyl branched paraffins; the mono-methyl branched paraffinscomprise less than about 30 wt % terminal branched isoparaffins; and theisoparaffins have a kinematic viscosity of less than about 10 cSt at 40°C. and have a biodegradability of at least about 40% after about 23 daysof exposure to microorganisms.

In some embodiments, the substance is a food crop, a metal, or wood. Insome embodiments, protecting involves solvating the substance. In suchembodiments, the substance includes pesticides, herbicides, paints,inks, or coatings. In some embodiments, protecting involves cleaning thesubstance with the paraffinic fluid In such embodiments, the substancecomprises fabric, metal, or plastic. In some embodiments, protectinginvolves lubricating the substance where the substance is metal.

In an aspect, a method is provided which involves producing an orificein a substrate by at least injecting a paraffinic fluid into thesubstrate, wherein the paraffinic fluid comprises a hydrodeoxygenatedproduct; the hydrodeoxygenated product is produced by hydrodeoxygenatinga bio-derived feed; the bio-derived feed comprising bio-derived fattyacids, fatty acid esters, or a combination thereof; thehydrodeoxygenated product comprises n-paraffins; the paraffinic fluidcontains less than about 1 wt % aromatics; and the n-paraffins have akinematic viscosity of less than about 10 cSt at 40° C. and have abiodegradability of at least about 40% after about 23 days of exposureto microorganisms. In some embodiments, the hydrodeoxygenated productincludes n-paraffins in the range of about 80 wt % to about 100 wt %;cycloparaffins in the range of about 1 wt % to about 10 wt %; and lessthan about 1 wt % total aromatics. In some embodiments, the paraffinicfluid further includes a hydroisomerized product produced by at leastpartially hydroisomerizing the hydrodeoxygenated product; wherein thehydroisomerized product comprises isoparaffins where at least about 80wt % of the isoparaffins are mono-methyl branched paraffins; themono-methyl branched paraffins comprise less than about 30 wt % terminalbranched isoparaffins; and the isoparaffins have a kinematic viscosityof less than about 10 cSt at 40° C. and have a biodegradability of atleast about 40% after about 23 days of exposure to microorganisms.

In some embodiments, the substrate comprises a soil substrate, a topsoilsubstrate, a subsoil substrate, a clay substrate, a sand substrate, arock substrate, or a stone substrate. In some embodiments, thebio-derived fatty acids, fatty acid esters, or a combination thereofcomprises algae oils, beef tallow, camelina oil, canola oil, rapeseedoil, castor oil, choice white grease, coconut oil, coffee bean oil, cornoil, cottonseed oil, fish oils, hemp oil, Jatropha oil, linseed oil,mustard oil, palm oil, palm kernel oil, poultry fat, soybean oil,sunflower oil, tall oil, tall oil fatty acid, Tung oil, used cookingoils, yellow grease, products of the food industry, or combinations ofany two or more thereof. In some embodiments, the bio-derived fattyacids, fatty acid esters, or a combination thereof comprise soybean oil,corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil, palmoil, palm kernel oil, rapeseed oil, or a combination of any two or morethereof. In some embodiments, the step of producing an orifice compriseshydraulic fracturing of the substrate with the paraffinic fluid.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 depicts a process for conversion of a bio-derived feed toindustrial fluids, the process comprising hydrodeoxygenation,hydroisomerization, peroxide-initiated oligomerization, andfractionation

DETAILED DESCRIPTION

Various embodiments are described hereinafter. It should be noted thatthe specific embodiments are not intended as an exhaustive descriptionor as a limitation to the broader aspects discussed herein. One aspectdescribed in conjunction with a particular embodiment is not necessarilylimited to that embodiment and can be practiced with any otherembodiment(s).

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the elements (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the embodiments and does not pose alimitation on the scope of the claims unless otherwise stated. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential.

In general, “substituted” refers to an alkyl or aryl group as definedbelow (e.g., an alkyl group) in which one or more bonds to a hydrogenatom contained therein are replaced by a bond to non-hydrogen ornon-carbon atoms. Substituted groups also include groups in which one ormore bonds to a carbon(s) or hydrogen(s) atom are replaced by one ormore bonds, including double or triple bonds, to a heteroatom. Thus, asubstituted group will be substituted with one or more substituents,unless otherwise specified. In some embodiments, a substituted group issubstituted with 1, 2, 3, 4, 5, or 6 substituents. Examples ofsubstituent groups include: halogens (i.e., F, Cl, Br, and I);hydroxyls; alkoxy, alkylperoxy, alkenoxy, alkynoxy, aryloxy, arylperoxy,aralkyloxy; carbonyls (oxo); carboxyls; esters; urethanes; oximes;hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides;sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides;hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines;guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates;thiocyanates; imines; nitro groups; nitriles (i.e., CN); and the like.

As used herein, “alkyl” groups include straight chain and branched alkylgroups having from 1 to about 20 carbon atoms, and typically from 1 to12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Asemployed herein, “alkyl groups” include cycloalkyl groups as definedbelow. Alkyl groups may be substituted or unsubstituted. Examples ofstraight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branchedalkyl groups include, but are not limited to, isopropyl, sec-butyl,t-butyl, neopentyl, and isopentyl groups. Representative substitutedalkyl groups may be substituted one or more times with, for example,amino, thio, hydroxy, cyano (i.e. CN), alkoxy, and/or halo groups suchas F, Cl, Br, and I groups.

Cycloalkyl groups are cyclic alkyl groups such as, but not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, andcyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8ring members, whereas in other embodiments the number of ring carbonatoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substitutedor unsubstituted. Cycloalkyl groups further include polycycliccycloalkyl groups such as, but not limited to, norbornyl, adamantyl,bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused ringssuch as, but not limited to, decalinyl, and the like. Cycloalkyl groupsalso include rings that are substituted with straight or branched chainalkyl groups as defined above. Representative substituted cycloalkylgroups may be mono-substituted or substituted more than once, such as,but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstitutedcyclohexyl groups or mono-, di-, or tri-substituted norbornyl orcycloheptyl groups, which may be substituted with, for example, alkyl,alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.

As used herein, “aryl” groups are cyclic aromatic hydrocarbons that donot contain heteroatoms. Aryl groups include monocyclic, bicyclic andpolycyclic ring systems. Thus, aryl groups include, but are not limitedto, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl,phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl,biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthylgroups. In some embodiments, aryl groups contain 6-14 carbons, and inothers from 6 to 12 or even 6-10 carbon atoms in the ring portions ofthe groups. The phrase “aryl groups” includes groups containing fusedrings, such as fused aromatic-aliphatic ring systems (e.g., indanyl,tetrahydronaphthyl, and the like). Aryl groups may be substituted orunsubstituted.

The term “microorganisms” as used herein refers to microbes capable ofdegrading hydrocarbons.

The term “paraffins” as used herein means branched or unbranchedhydrocarbon alkanes. An unbranched paraffin is an n-paraffin; a branchedparaffin is an isoparaffin.

The term “paraffinic” as used herein means both paraffins as definedabove as well as predominantly hydrocarbon chains possessing regionsthat are alkane, either branched or unbranched, with mono- ordi-unsaturation (i.e. one or two double bonds), halogenation from about30 wt % to about 70 wt %, or where the hydrocarbon is both unsaturatedand halogenated. However, the term does not describe a halogen on acarbon involved in a double bond.

The phrase “C₂+ chain branching” as used herein means alkyl brancheswherein the alkyl group has two or more carbons; e.g. ethyl or isopropylbranches.

“Protecting” as used herein includes, but is not limited to, solvating,coating, cleaning, lubricating, or preserving a substance, surface, orcomposition.

“Orifice” as used herein encompasses holes, channels, fractures, andfissure; in other words, the term encompasses spaces of anythree-dimensional length, width, and diameter that are not filled withsolid material.

The present technology provides bio-based synthetic fluids as well asmethods for making the fluids and methods that utilize the advantageousproperties of the bio-based synthetic fluids, as discussed herein.

In an aspect, a method is provided involving altering the viscosity ofbio-derived paraffins to produce a paraffinic fluid, where the alteringstep includes oligomerizing bio-derived paraffins, unsaturatingbio-derived paraffins, chlorinating bio-derived paraffins, or acombination of any two or more thereof; the bio-derived paraffins areproduced by hydrodeoxygenating a bio-based feed; the bio-based feedcomprises bio-derived fatty acids, fatty acid esters, or a combinationthereof; the bio-derived paraffins comprise n-paraffins; and then-paraffins have a biodegradability of at least about 40% after about 23days of exposure to microorganisms. The biodegradability may be about42%, about 44%, about 46%, about 48%, about 50%, about 52%, about 54%,about 56%, about 58%, about 60%, about 62%, about 64%, about 66%, about68%, about 70%, about 72%, about 74%, about 76%, about 78%, about 80%,and ranges between any two of these values or greater than any one ofthese values. In some embodiments, the paraffinic fluid contains belowabout 1 wt % total aromatics. The paraffinic fluid may contain aromaticsin the amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt%, about 0.1 wt %, and ranges between any two of these values or belowany one of these values. In some embodiments, the paraffinic fluidcontain less than 0.1 wt % total aromatics. In some embodiments, theparaffinic fluid is free of benzene.

In some embodiments, the paraffinic fluid has a kinematic viscosity lessthan about 10 cSt at 40° C. In such embodiments, the paraffinic fluidmay have a kinematic viscosity at 40° C. of about 9 cSt, about 8 cSt,about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2cSt, about 1 cSt, and ranges in between any two of these values or belowany one of these values. In some embodiments, the paraffinic fluid has akinematic viscosity greater than about 10 cSt at 40° C. In suchembodiments, the paraffinic fluid may have a kinematic viscosity at 40°C. of about 12 cSt, about 14 cSt, about 16 cSt, about 18 cSt, about 20cSt, about 22 cSt, about 24 cSt, about 26 cSt, about 28 cSt, about 30cSt, and ranges in between any two of these values or greater than anyone of these values. In some embodiments, the paraffinic fluid has akinematic viscosity greater than about 20 cSt at 40° C.

Bio-Based Feed:

Bio-derived fatty acids, fatty acid esters, or combinations thereof, areutilized as the bio-based feed for making the fluids describedthroughout this application. The bio-derived fatty acids, fatty acidesters, or combinations thereof include algae oils, beef tallow,camelina oil, canola/rapeseed oil, castor oil, choice white grease,coconut oil, coffee bean oil, corn oil, fish oils, hemp oil, Jatrophaoil, linseed oil, mustard oil, palm oil, poultry fat, soybean oil,sunflower oil, tall oil, tall oil fatty acid, Tung oil, used cookingoils, yellow grease, products of the food industry, or combinations ofany two or more thereof. In some embodiments, the bio-derived fattyacids, fatty acid esters, or combinations thereof include soybean oil,corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil, palmoil, palm kernel oil, rapeseed oil, or a combination of any two or morethereof.

In their natural form, most of these fats and oils contain phosphorus aswell as metals such as calcium, magnesium, sodium, potassium, iron, andcopper. Additionally, most also contain nitrogen compounds such aschlorophyll or amino acids. When the level of phosphorus is greater thanabout 40 wppm, and total metals greater than about 30 wppm, the fats andoils may be subjected to treatment steps including, but not limited to,acid degumming, neutralization, bleaching, or a combination of any twoor more thereof. Acid degumming involves contacting the fat/oil withconcentrated aqueous acids. Exemplary acids are phosphoric, citric, andmaleic acids. This pretreatment step removes metals such as calcium andmagnesium in addition to phosphorus. Neutralization is typicallyperformed by adding a caustic (referring to any base, such as aqueousNaOH) to the acid-degummed fat/oil. The process equipment used for aciddegumming and neutralization includes high shear mixers and disk stackcentrifuges.

Bleaching typically involves contacting the degummed fat/oil withadsorbent clay and filtering the spent clay through a pressure leaffilter. Use of synthetic silica instead of clay is reported to provideimproved adsorption. The bleaching step removes chlorophyll and much ofthe residual metals and phosphorus. Any soaps that may have been formedduring the caustic neutralization step (i.e. by reaction with free fattyacids) are also removed during the bleaching step. The aforementionedtreatment processes are known in the art and described in the patentliterature, including but not limited to U.S. Pat. Nos. 4,049,686,4,698,185, 4,734,226, and 5,239,096. It should be recognized by thoseskilled in the art that other fat/oil treatment methods, including thoseinvolving alternate physical, thermal, and chemical processes, may beadapted to pretreatment of a bio-based feed.

Hydrodeoxygenation:

The bio-based feed is subjected to hydrodeoxygenation (HDO) in acatalytic reactor wherein the fatty acids and/or fatty acid esters areconverted to straight-chain paraffins. In hydrodeoxygenation, the oxygenatoms of the fatty acid/ester are removed through hydrogenolysis to formwater, while the unsaturated carbon-carbon double bonds of the fattyacid chains are simultaneously hydrogenated. HDO may be accompanied bydecarbonylation and decarboxylation reactions (wherein the oxygen atomis removed as CO and CO₂ respectively). The HDO reaction takes place attemperatures from about 200° C. to about 400° C., and hydrogen partialpressure between about 20 bar to about 160 bar. The HDO reaction mayoccur at a temperature of about 220° C., 240° C., 260° C., 280° C., 300°C., 320° C., 340° C., 360° C., 380° C., and ranges between any two ofthese values or above any one of these values. In some embodiments,temperature range is from about 260° C. to about 370° C. The HDOreaction may occur at a hydrogen partial pressure of about 30 bar, 40bar, 50 bar, 60 bar, 70 bar, 80 bar, 90 bar, 100 bar, 110 bar, 120 bar,130 bar, 140 bar, 150 bar, and ranges between any two of these values orabove any one of these values. In some embodiments, the pressure rangeis from about 30 bar to about 130 bar. Suitable catalysts for the HDOprocess include sulfided forms of hydrogenation metals from Group VIBand Group VIII of the periodic table. Examples of suitablemono-metallic, bi-metallic, and tri-metallic catalysts include Mo, Ni,Co, W, CoMo, NiMo, NiW, NiCoMo. These catalysts may be supported onalumina, or alumina modified with oxides of silicon and/or phosphorus.These catalysts may be purchased in the reduced sulfide form, or morecommonly purchased as metal oxides and sulfided during startup. Toensure these catalysts remain in the reduced sulfide form required fordesired activity/selectivity balance, use of a “sulfur spike” compoundsuch as dimethyl disulfide may be utilized. Fixed-bed and/or slurryreactor systems and operating conditions may be used. In someembodiments, continuous reactor systems are used. In some embodiments,continuous fixed-bed reactors are used. In continuous fixed-bed reactorsystems, the liquid hourly space velocity (LHSV) is between about 0.2h⁻¹ and about 10 h⁻¹, and the hydrogen gas-to-oil ratio (GOR at standardconditions) is between about 200 NL/L and about 1600 NL/L. The LHSV maybe about 0.3 h⁻¹, about 0.4 h⁻¹, about 0.5 h⁻¹, about 0.6 h⁻¹, about 0.7h⁻¹, about 0.8 h⁻¹, about 0.9 h⁻¹, about 1.0 h⁻¹, about 1.2 h⁻¹, about1.4 h⁻¹, about 1.6 h⁻¹, about 1.8 h⁻¹, about 2.0 h⁻¹, about 2.2 h⁻¹,about 2.4 h⁻¹, about 2.6 h⁻¹, about 2.8 h⁻¹, about 3.0 h⁻¹, about 3.0h⁻¹, about 3.2 h⁻¹, about 3.4 h⁻¹, about 3.6 h⁻¹, about 3.8 h⁻¹, about4.0 h⁻¹, about 4.2 h⁻¹, about 4.4 h⁻¹, about 4.6 h⁻¹, about 4.8 h⁻¹,about 5.0 h⁻¹, about 5.2 h⁻¹, about 5.4 h⁻¹, about 5.6 h⁻¹, about 5.8h⁻¹, about 6.0 h⁻¹, about 6.2 h⁻¹, about 6.4 h⁻¹, about 6.6 h⁻¹, about6.8 h⁻¹, about 7.0 h⁻¹, about 7.2 h⁻¹, about 7.4 h⁻¹, about 7.6 h⁻¹,about 7.8 h⁻¹, about 8.0 h⁻¹, about 8.2 h⁻¹, about 8.4 h⁻¹, about 8.6h⁻¹, about 8.8 h⁻¹, about 9.0 h⁻¹, about 9.2 h⁻¹, about 9.4 h⁻¹, about9.6 h⁻¹, about 9.8 h⁻¹, and ranges between any two of these values orabove any one of these values. In some embodiments with continuousfixed-bed reactor systems, the LHSV is from about 0.5 h⁻¹ to about 5.0h⁻¹. The GOR may be about 250 NL/L, 300 NL/L, 350 NL/L, 400 NL/L, 450NL/L, 500 NL/L, 550 NL/L, 600 NL/L, 650 NL/L, 700 NL/L, 750 NL/L, 800NL/L, 850 NL/L, 900 NL/L, 950 NL/L, 1000 NL/L, 1050 NL/L, 1100 NL/L,1150 NL/L, 1200 NL/L, 1250 NL/L, 1300 NL/L, 1350 NL/L, 1400 NL/L, 1450NL/L, 1500 NL/L, 1550 NL/L, and ranges between any two of these valuesor above any one of these values. In some embodiments with continuousfixed-bed reactor systems, GOR is from about 400 NL/L to about 1400NL/L.

The reactor effluent is directed to a high pressure separator forseparating the gas stream containing unreacted hydrogen and gas phasebyproducts such as water, CO, CO₂, H₂S, NH₃, and propane from the liquidHDO products. The gas is then cooled and directed to a three-phase coldseparator drum. There a water stream with dissolved carbonate,bisulfide, and ammonium salts, a hydrocarbon stream containing lighthydrocarbons, and a hydrogen rich gas stream are separated. The hydrogenrich gas is optionally scrubbed to remove the gas phase byproducts andrecycled to the reactor. The liquid HDO product from the high pressureseparator may also be partially recycled to the reactor to dilute thereactive bio-based feed to the exothermic HDO reactor.

Those skilled in the art recognize that variations to these operatingconditions may be made based on purity of available hydrogen gas and toensure proper three-phase (H₂ gas/liquid feed/solid catalyst) contactingregime within the reactor. The liquid paraffin product compositionobtained from subjecting most fatty acid/ester bio-based feeds to HDO isa hydrocarbon composition rich in n-paraffins in the C₁₁ to C₂₂ range.The HDO product contains between about 80 wt % and 100 wt % n-paraffins,between about 0 wt % and about 20 wt % isoparaffins, between about 0 wt% and about 10 wt % cycloparaffins (also called naphthenes ornaphthenics), between about 0 wt % and about 10% wt % olefins, and belowabout 1 wt % total aromatics. It is important to note that the methoddoes not involve more severe aromatic hydrogenation conditions. The HDOproduct may contain n-paraffins in the amount of about 82 wt %, about 84wt %, about 86 wt %, about 88 wt %, about 90 wt %, about 92 wt %, about94 wt %, about 96 wt %, about 98 wt %, and ranges between any two ofthese values or above any one of these values. The n-paraffins have abiodegradability of at least about 40% after about 23 days of exposureto microorganisms. The biodegradability may be about 42%, about 44%,about 46%, about 48%, about 50%, about 52%, about 54%, about 56%, about58%, about 60%, about 62%, about 64%, about 66%, about 68%, about 70%,about 72%, about 74%, about 76%, about 78%, about 80%, and rangesbetween any two of these values or greater than any one of these values.The n-paraffins have a kinematic viscosity of less than about 10 cSt at40° C. The n-paraffins may have a kinematic viscosity at 40° C. of about9 cSt, about 8 cSt, about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt,about 3 cSt, about 2 cSt, about 1 cSt, and ranges in between any two ofthese values or below any one of these values.

The HDO product may contain cycloparaffins in the amount of about 1 wt%, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, and ranges between any two ofthese values or below any one of these values. The HDO product maycontain aromatics in the amount of about 0.9 wt %, about 0.8 wt %, about0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt%, about 0.2 wt %, about 0.1 wt %, and ranges between any two of thesevalues or below any one of these values. In some embodiments, the HDOproduct contains less than 0.1 wt % total aromatics. In someembodiments, the HDO product is free of benzene. The HDO product has akinematic viscosity of less than about 10 cSt at 40° C. The HDO productmay have a kinematic viscosity at 40° C. of about 9 cSt, about 8 cSt,about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2cSt, about 1 cSt, and ranges in between any two of these values or belowany one of these values.

The HDO product may be distilled to yield a synthetic renewable drillingbase fluid in the C₁₆-C₁₈ range. This fluid has a flash point greaterthan about 100° C., a kinematic viscosity in the range of about 3 cSt toabout 4 cSt at 40° C., a pour point of about 16° C. to about 20° C.,high thermal and oxidative stability due to paraffinic structure (i.e.having a total insoluble content of 0.2 mg/100 mL or less according tothe ASTM D2274 accelerated oxidative aging method when 20 wppm or moreanti-oxidant is added to the fluid), low aquatic toxicity andecotoxicity (i.e. having an LC₅₀ value of 3.5 mg/L or higher where LC₅₀is the concentration at which half a population of the organism dies ofingesting the fluid, and is typically the average of 24 hour, 48 hour,and 72 hour exposure tests on Daphia magna, Pimephales promelas, orRainbow Trout), and a biodegradability greater than about 40% accordingto ASTM D5864-05, incorporated herein by reference. ASTM D5864-05measures how much of a material breaks down into CO₂ by microorganismsover a period of 23 days. In contrast to the paraffins of thisapplication, typical petroleum-based mineral oils have biodegradabilityin the 15-35% range, while synthetic oils like poly alpha-olefins (PAOs)have biodegradability in the 5-30% range. Organic compounds with lowbiodegradability (i.e. less than about 40% biodegradability) are said tobioaccumulate. Bioaccumulation tends to magnify the toxic effect ofchemicals on the environment.

Hydroisomerization of Bio-Based Paraffins:

The HDO paraffins may be subjected to hydroisomerization to provide ahydroisomerized product. The hydroisomerized product includesmethyl-branched paraffins in the C₁₆-C₁₈ range with low pour point, highthermal/oxidative stability, and low ecotoxicity. Hydroisomerization isconducted over a bifunctional catalyst at temperatures in the range ofabout 200° C. to about 500° C. The hydroisomerization may be conductedat a temperature of about 220° C., about 240° C., about 260° C., about280° C., about 300° C., about 320° C., about 340° C., about 360° C.,about 380° C., about 400° C., about 420° C., about 440° C., about 460°C., about 480° C., and ranges between any two of these values or aboveany one of these values. Bifunctional catalysts are those having ahydrogenation-dehydrogenation activity from a Group VIB and/or GroupVIII metal, and acidic activity from an amorphous or crystalline supportsuch as amorphous silica-alumina (ASA), silicon-aluminum-phosphate(SAPO) molecular sieve, or aluminum silicate zeolite (ZSM). In someembodiments, the hydroisomerization catalysts include Pt/Pd-on-ASA, andPt-on-SAPO-11.

In some embodiments, hydroisomerization is conducted in continuousfixed-bed reactors. In such embodiments, the hydrogen partial pressurefor hydroisomerization is in the range between about 30 bar and about160 bar, GORs are in the range of about 100 NL/L to about 1,000 NL/L,and LHSV in the range from about 0.2 hr⁻¹ to about 5 hr⁻¹. In someembodiments, the hydrogen partial pressure for hydroisomerization isabout 40 bar, about 50 bar, about 60 bar, about 70 bar, about 80 bar,about 90 bar, about 100 bar, about 110 bar, about 120 bar, about 130bar, about 140 bar, about 150 bar, and ranges between any two of thesevalues or above any one of these values. In some embodiments, the GORmay be about 150 NL/L, about 200 NL/L, about 250 NL/L, 300 NL/L, 350NL/L, 400 NL/L, 450 NL/L, 500 NL/L, 550 NL/L, 600 NL/L, 650 NL/L, 700NL/L, 750 NL/L, 800 NL/L, 850 NL/L, 900 NL/L, 950 NL/L, and rangesbetween any two of these values or above any one of these values. TheLHSV may be about 0.3 h⁻¹, about 0.4 h⁻¹, about 0.5 h⁻¹, about 0.6 h⁻¹,about 0.7 h⁻¹, about 0.8 h⁻¹, about 0.9 h⁻¹, about 1.0 h⁻¹, about 1.2h⁻¹, about 1.4 h⁻¹, about 1.6 h⁻¹, about 1.8 h⁻¹, about 2.0 h⁻¹, about2.2 h⁻¹, about 2.4 h⁻¹, about 2.6 h⁻¹, about 2.8 h⁻¹, about 3.0 h⁻¹,about 3.0 h⁻¹, about 3.2 h⁻¹, about 3.4 h⁻¹, about 3.6 h⁻¹, about 3.8h⁻¹, about 4.0 h⁻¹, about 4.2 h⁻¹, about 4.4 h⁻¹, about 4.6 h⁻¹, about4.8 h⁻¹, and ranges between any two of these values or above any one ofthese values.

In an embodiment, the HDO product is hydroisomerized according to theconditions described herein using Pt/SAPO-11 catalyst. Thehydroisomerizate is preferably stripped of light hydrocarbons in orderto raise the flash point above 60° C. The flash point may be above 70°C., above 80° C., above 90° C., or above 100° C. The hydroisomerizedproduct has a ratio of isoparaffins-to-normal paraffins in the range ofabout 1:1 to about 30:1. The ratio of isoparaffins-to-normal paraffinsmay be about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1,about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1,about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1,about 20:1, about 21:1, about 22:1, about 23:1, about 24:1, about 25:1,about 26:1, about 27:1, about 28:1, about 29:1, and ranges between anytwo of these values or above any one of these values. In someembodiments, the ratio of isoparaffins-to-normal paraffins is betweenabout 5:1 and about 20:1. In the hydroisomerized product at least 80 wt% of the isoparaffins are mono-methyl branched paraffins. Themono-methyl branched paraffins may be about 81 wt %, about 82 wt %,about 83 wt %, about 84 wt %, about 85 wt %, about 86 wt %, about 87 wt%, about 88 wt %, about 89 wt %, about 90 wt %, about 91 wt %, about 92wt %, about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt %, about97 wt %, about 98 wt %, about 99 wt %, and ranges between any two ofthese values or above any one of these values. Examples of themono-methyl branched paraffins in the hydroisomerized HDO productinclude 4-methyl heptadecane, 3-methyl hexadecane, and 2-methylpentadecane. Of the mono-methyl branched isoparaffins, less than 30 wt %are terminal branched (i.e. 2-methyl branched). In some embodiments,less than 20 wt % of the mono-methyl branched isoparaffins are terminalbranched. In some embodiments, less than 15 wt % of the mono-methylbranched isoparaffins are terminal branched. In some embodiments, lessthan 10 wt % of the mono-methyl branched isoparaffins are terminalbranched. In some embodiments, less than 5 wt % of the mono-methylbranched isoparaffins are terminal branched. It is important to notethat the method does not involve more severe aromatic hydrogenationconditions.

The isoparaffins have a biodegradability of at least about 40% afterabout 23 days of exposure to microorganisms. The biodegradability may beabout 42%, about 44%, about 46%, about 48%, about 50%, about 52%, about54%, about 56%, about 58%, about 60%, about 62%, about 64%, about 66%,about 68%, about 70%, about 72%, about 74%, about 76%, about 78%, about80%, and ranges between any two of these values or greater than any oneof these values. The isoparaffins have a kinematic viscosity of lessthan about 10 cSt at 40° C. The isoparaffins may have a kinematicviscosity at 40° C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1 cSt,and ranges in between any two of these values or below any one of thesevalues.

The hydroisomerized product may contain aromatics in the amount of about0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt%, about 0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, andranges between any two of these values or below any one of these values.In some embodiments, the hydroisomerized product contains less than 0.1wt % total aromatics. In some embodiments, the hydroisomerized productis free of benzene. The hydroisomerized product has a kinematicviscosity of less than about 10 cSt at 40° C. The hydroisomerizedproduct has a kinematic viscosity of less than about 10 cSt at 40° C.The hydroisomerized product may have a kinematic viscosity at 40° C. ofabout 9 cSt, about 8 cSt, about 7 cSt, about 6 cSt, about 5 cSt, about 4cSt, about 3 cSt, about 2 cSt, about 1 cSt, and ranges in between anytwo of these values or below any one of these values.

Due the presence of mostly internal mono-methyl branched paraffins, thehydroisomerized HDO product of this technology has an excellent balanceof properties for use as drilling and/or hydraulic fracturing fluids.The pour point of the hydroisomerized fluid of this embodiment is atmost −10° C. The pour point may be at most about −15° C., at least about−20° C., at most about −25° C., at most about −30° C., at most about−35° C., at most about −40° C., or at most about −45° C. Thethermo-oxidative stability of the fluid may be measured by amount ofinsolubles formed upon heating and reported as mg/100 mL according toASTM D2274. For example, the stability thus measured can be as high as20 mg/100 mL for fluids with inferior oxidative stability properties,such as fatty acid esters. The lower the concentration of insolublesformed, the higher the thermo-oxidative stability of the fluid. The ASTMD2274 oxidative stability of the fluid produced by hydroisomerization ofthe HDO product as described herein is between about 0 mg/100 mL andabout 2 mg/100 mL upon addition of up to 20 wppm anti-oxidant. Preferredanti-oxidants for the bio-based hydrocarbon fluids of this technologyare hindered phenols, such as butyrated hydroxy toluene (BHT). Otherexamples of suitable anti-oxidants for the bio-based synthetichydrocarbon fluids of this invention include2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2- and3-t-butyl-4-hydroxyanisol (BHA), 2,6-distyrenated p-cresol,2,6-di-t-butylphenol, 2,6-di-t-butyl-4-sec-butylphenol,2,6-di-t-butyl-4-nonylphenol,2,4-bis-(n-octylthio)-6-(4-hydroxy-3′,5′-di-t-butylanilino)-1,3,5-triazine,2,4-bis-(octylthiomethyl)-6-methylphenol, 2,6-di-t-butyl-4-ethylphenol,2,4-dimethyl-6-t-butylphenol, the butylated reaction product of p-cresoland dicylcopentadiene, the mixed methylenic bridged adducts of alkylatedphenol and dodecane thiol, tetrakis methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) benzene,tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, and mixtures of anytwo or more thereof of the recited anti-oxidants.

Chlorinating Bio Based Paraffins:

Paraffin chlorination according to the present technology is one way ofincreasing the viscosity of a paraffinic fluid while reducingcrystallinity and hence lowering the paraffin pour point. For example,the HDO product does not have the required viscosity and pour point foruse, by itself, in such industrial processing fluid applications asmetal-working.

The HDO product and/or the hydroisomerized product may be chlorinated ina batch reactor by sparging pure chlorine gas into the liquid at atemperature in the range between about 60° C. and about 150° C. Thetemperature of the chlorination reaction may be about 65° C., about 70°C., about 80° C., about 85° C., about 90° C., about 95° C., about 100°C., about 105° C., about 110° C., about 115° C., about 120° C., about125° C., about 130° C., about 140° C., about 145° C., and ranges inbetween any two of these values or greater than any one of these values.In some embodiments, the temperature is in the range between about 80°C. and about 120° C. Chlorination is an exothermic reaction and coolingis necessary. Generally catalysts are not necessary at thesetemperatures, but in some embodiments UV light is used to accelerate thereaction. Once the desired degree of chlorination, typically betweenabout 30 wt % and about 70 wt %, and viscosity has been achieved, thechlorine supply is discontinued and the reactor purged with air ornitrogen to remove excess chlorine and hydrochloric acid gas.Hydrochloric acid is a co-product of the paraffin chlorination process.

The chlorinated paraffins, i.e. the chlorinated product, can be used asan industrial process fluid for metal-working lubricants, asplasticizers, flame-retardants, and fat liquors for leather.Plasticizers are generally used to make rigid polymers like PVC soft andrubbery. Addition of chlorinated paraffins also imparts flame-retardancyto the polymer compound. Fat liquors are fluids that are used to improvethe life and appearance of articles made of leather, such as jackets,handbags, and shoes. In some embodiments, the chlorinated product isused as a protecting agent, a cleaning agent, or a combination of both.In some embodiments, the chlorinated product acts as a flame retardant.In some embodiments, the chlorinated product is used to clean fabric,metal, or plastic.

The chlorinated product has a kinematic viscosity of greater than about10 cSt at 40° C. The chlorinated product may have a kinematic viscosityat 40° C. of about 12 cSt, about 14 cSt, about 16 cSt, about 18 cSt,about 20 cSt, about 22 cSt, about 24 cSt, about 26 cSt, about 28 cSt,about 30 cSt, and ranges in between any two of these values or greaterthan any one of these values. The chlorinated product is between about30 wt % and about 70 wt % chlorine in the form of chlorine covalentlybound to carbon. The amount of covalently bonded chlorine in thechlorinated product may be about 35 wt %, about 40 wt %, about 45 wt %,about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, and rangesbetween any two of these values or greater than any one of these values.The chlorinated product has less than about 1 wt % aromatics. Thechlorinated product may contain aromatics in the amount of about 0.9 wt%, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and rangesbetween any two of these values or below any one of these values. Insome embodiments, the chlorinated product contains less than 0.1 wt %total aromatics. In some embodiments, the chlorinated product is free ofbenzene. In some embodiments, the chlorinated product is used as aprotecting agent, a cleaning agent, or a combination of both. In someembodiments, the chlorinated product acts as a flame retardant. In someembodiments, the chlorinated product is used to clean fabric, metal, orplastic.

Dehydrochlorination of Bio Derived Paraffins:

The chlorinated products may optionally be subjected todehydrochlorination, wherein the chlorine is removed as hydrochloricacid. As an example, in embodiments where the chlorinated product isexclusively made from the HDO product, dehydrochlorination yields alinear olefin composition having a carbon number range similar to theHDO paraffin. The dehydrochlorination reaction takes place over silicaor bauxite at temperatures in the 360° C.-700° C. range. The reactionmay take place at a temperature of about 380° C., about 400° C., about420° C., about 440° C., about 460° C., about 480° C., about 500° C.,about 550° C., about 600° C., about 650° C., and ranges in between anytwo of these values or above any one of these values. In someembodiments, the reaction takes place at temperature in the range fromabout 400° C. to about 600° C. Dehydrochlorination may proceed in therange from about 68% conversion to about 100% conversion.Dehydrochlorination can proceed to about 70% conversion, about 75%conversion, about 80% conversion, about 85% conversion, about 90%conversion, about 95% conversion, about 98% conversion, about 99%conversion, and ranges in between any two of these values or above anyone of these values. As such, the dehydrochlorination reactor productfrom dehydrochlorination of the HDO product is a C₁₆/C₁₈ linearhydrocarbon composition comprising up to 100% internal olefins,characterized by higher biodegradability than saturated hydrocarbons.This olefinic composition has a lower pour point and higher lubricitythan the equivalent paraffin composition, making it particularlywell-suited for drilling and hydraulic fracturing fluid formulations.

The olefinic composition has a biodegradability of at least about 40%after about 23 days of exposure to microorganisms. The biodegradabilitymay be about 42%, about 44%, about 46%, about 48%, about 50%, about 52%,about 54%, about 56%, about 58%, about 60%, about 62%, about 64%, about66%, about 68%, about 70%, about 72%, about 74%, about 76%, about 78%,about 80%, and ranges between any two of these values or greater thanany one of these values. The olefinic composition has a kinematicviscosity of less than about 10 cSt at 40° C. The olefinic compositionmay have a kinematic viscosity at 40° C. of about 9 cSt, about 8 cSt,about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2cSt, about 1 cSt, and ranges in between any two of these values or belowany one of these values. The olefinic composition may contain aromaticsin the amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt%, about 0.1 wt %, and ranges between any two of these values or belowany one of these values. In some embodiments, the olefinic compositioncontains less than 0.1 wt % total aromatics. In some embodiments, theolefinic composition is free of benzene. In some embodiments, theolefinic composition is used as a hydraulic fracturing fluid, as adrilling fluid, or a combination of the two.

Dehydrogenation of Bio-Derived Paraffins:

The paraffinic fluid, for example the HDO product and/or thehydroisomerization product, may be subjected to dehydrogenation toproduce a olefinic fluid with an improved balance of biodegradability,lubricity, thermo-oxidative stability, ecotoxicity, and pour point, fordrilling base fluids. The reaction takes place at a temperature in therange from about 360° C. to about 660° C. The reaction may take place atabout 380° C., about 400° C., about 420° C., about 440° C., about 460°C., about 480° C., about 500° C., about 520° C., about 540° C., about560° C., about 580° C., about 600° C., about 620° C., about 640° C., andranges between any two of these values or above any one of these values.In some embodiments, the reaction takes place in a temperature in therange from about 440° C. to about 580° C. The reaction is endothermicand is favored at low pressures. Typical operating pressures are in therange from about 1 bar to about 20 bar. The operating pressure may beabout 2 bar, about 3 bar, about 4 bar, about 5 bar, about 6 bar, about 7bar, about 8 bar, about 9 bar, about 10 bar, about 11 bar, about 12 bar,about 13 bar, about 14 bar, about 15 bar, about 16 bar, about 17 bar,about 18 bar, about 19 bar, and ranges between any two of these valuesor above any one of these values. In some embodiments, the operatingpressure is from about 2 bar to about 12 bar. At these conditions, thehydrocarbons are in vapor phase. Generally base metals and noble metalcatalysts from Groups VIB and VIII that havehydrogenation-dehydrogenation activity provide a low activation energymechanism for paraffin dehydrogenation. Such metals include Pt, Pd, Rh,Ru, Ir, Os, and Re. The reaction is carried out in gas phase at hightemperatures and low pressures. Preferred catalyst systems for paraffindehydrogenation include alkali and alkaline earth metal promoters aswell. A preferred catalyst for the system is platinum/lithium onalumina.

In an embodiment, the HDO paraffins are pressurized to about 10 bar andpreheated to about 580° C. before entering a dehydrogenation reactor. Itis important to note that the conditions provided in this embodiment areapplicable to the dehydrogenation of the hydroisomerized productdescribed earlier. The reactor is packed with Pt/Li-on-alumina catalyst.The reactor geometry is selected to provide low pressure drop whileensuring sufficient contact time to achieve desired conversion, andpreferably approach the thermodynamic equilibrium conversion for theendothermic reactions. Preferred contact times are expressed by liquidhourly space velocities (LHSV) in the range of about 1 h⁻¹ to about 10h⁻¹. The LHSV may be about 1.2 h⁻¹, about 1.4 h⁻¹, about 1.6 h⁻¹, about1.8 h⁻¹, about 2.0 h⁻¹, about 2.2 h⁻¹, about 2.4 h⁻¹, about 2.6 h⁻¹,about 2.8 h⁻¹, about 3.0 h⁻¹, about 3.0 h⁻¹, about 3.2 h⁻¹, about 3.4h⁻¹, about 3.6 h⁻¹, about 3.8 h⁻¹, about 4.0 h⁻¹, about 4.2 h⁻¹, about4.4 h⁻¹, about 4.6 h⁻¹, about 4.8 h⁻¹, about 5.0 h⁻¹, about 5.2 h⁻¹,about 5.4 h⁻¹, about 5.6 h⁻¹, about 5.8 h⁻¹, about 6.0 h⁻¹, about 6.2h⁻¹, about 6.4 h⁻¹, about 6.6 h⁻¹, about 6.8 h⁻¹, about 7.0 h⁻¹, about7.2 h⁻¹, about 7.4 h⁻¹, about 7.6 h⁻¹, about 7.8 h⁻¹, about 8.0 h⁻¹,about 8.2 h⁻¹, about 8.4 h⁻¹, about 8.6 h⁻¹, about 8.8 h⁻¹, about 9.0h⁻¹, about 9.2 h⁻¹, about 9.4 h⁻¹, about 9.6 h⁻¹, about 9.8 h⁻¹, andranges between any two of these values or above any one of these values.It should be noted that although space velocities are expressed in termsof liquid feed, in some embodiments of the dehydrogenation conditionsthe reactor feed and products are in the vapor phase. In someembodiments, a plurality of reactors is configured in series, withprovisions for heating each reactor feed. In some embodiments, betweenabout 5 wt % and about 40 wt % of the HDO n-paraffins are converted tolinear olefins. The conversion of HDO n-paraffins to linear olefins maybe about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30wt %, about 35 wt %, and ranges in between any two of these values orabove any one of these values. In some embodiments, between about 10 wt% and about 30 wt % of the HDO n-paraffins are converted to linearolefins. The reactor effluent is cooled to condense a linear hydrocarbonproduct composition from hydrogen, where the linear hydrocarbon productcomposition is primarily in the C₁₆-C₁₈ range. The hydrogen may bepartially recycled to the reactor to mitigate coking in the reactor. Ahydrogen-to-hydrocarbon mole ratio of about 1:1 to about 20:1 isutilized. The hydrogen-to-hydrocarbon mole ratio may be about 2:1, about3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1,about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1,about 16:1, about 17:1, about 18:1, about 19:1, and ranges between anytwo of these values or above any one of these values. In someembodiments, the hydrogen-to-hydrocarbon mole ratio is from about 8:1 toabout 12:1.

The liquid product of this embodiment of the dehydrogenation of the HDOproduct is a straight-chain hydrocarbon composition comprising ofn-paraffins and linear olefins. The composition comprises 50-90 wt %n-paraffins in the C₁₆-C₁₈ range, 10-40 wt % C₁₆-C₁₈ linear internalolefins in the C₁₆-C₁₈ range, and 0-10 wt % linear alpha olefins in theC₁₆-C₁₈ range. The composition may have n-paraffins in the C₁₆-C₁₈ rangein the amount of about 55 wt %, about 60 wt %, about 65 wt %, about 70wt %, about 75 wt %, about 80 wt %, about 85 wt %, and ranges in betweenany two of these values or below any one of these values. Thecomposition may have linear internal olefins in the C₁₆-C₁₈ range in theamount of about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %,about 35 wt %, and ranges between any two of these values or above anyone of these values. The composition may have linear alpha olefins inthe C₁₆-C₁₈ range in the amount of about 0 wt % to about 5 wt % or about5 wt % to about 10 wt %.

Due the presence of linear internal olefins, the pour point of thestraight-chain hydrocarbon composition is lowered. Compared to fullysaturated hydrocarbons, this composition offers superiorbiodegradability, making it attractive as a drilling base fluid.

The olefinic fluid has a biodegradability of at least about 40% afterabout 23 days of exposure to microorganisms. The biodegradability may beabout 42%, about 44%, about 46%, about 48%, about 50%, about 52%, about54%, about 56%, about 58%, about 60%, about 62%, about 64%, about 66%,about 68%, about 70%, about 72%, about 74%, about 76%, about 78%, about80%, and ranges between any two of these values or greater than any oneof these values. The olefinic fluid has a kinematic viscosity of lessthan about 10 cSt at 40° C. The olefinic fluid may have a kinematicviscosity at 40° C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1 cSt,and ranges in between any two of these values or below any one of thesevalues. The olefinic fluid of the present technology may containaromatics in the amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt%, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about0.2 wt %, about 0.1 wt %, and ranges between any two of these values orbelow any one of these values. In some embodiments, the olefinic fluidcontains less than 0.1 wt % total aromatics. In some embodiments, theolefinic fluid is free of benzene. In some embodiments, the olefinicfluid is used as a hydraulic fracturing fluid, as a drilling fluid, or acombination of the two.

Acid-Catalyzed Oligomerization:

It is to be understood that the term “oligomerization” as used hereinrefers to the formation of a compound from 2, 3, 4, 5, 6, 7, 8, 9 or 10monomers, where the compound formed by oligomerization is an “oligomer”or an “oligomerized product.” For example, a dimer is a compound madefrom the oligomerization of 2 monomers, a trimer is a compound made fromthe oligomerization of 3 monomers, and a tetramer is a compound madefrom the oligomerization of 4 monomers. The olefins produced bydehydrogenation of the bio-derived paraffins or by dehydrochlorinationof the chlorinated product, described above, can be oligomerized toproduce fluids having a higher average molecular weight, higher boilingrange, and higher viscosity. Since most of the carbon-carbon doublebonds in the linear olefins are mainly in the internal positions (asindicated in the aforementioned section describing the internalolefins), the branched dimers are characterized by mainly C₂+ chainbranching. Such fluids, having a kinematic viscosity greater than about10 cSt at 40° C. are excellently suited for various mineral oil andlubricating oil applications. The oligomerized product may have akinematic viscosity at 40° C. of about 12 cSt, about 14 cSt, about 16cSt, about 18 cSt, about 20 cSt, about 22 cSt, about 24 cSt, about 26cSt, about 28 cSt, about 30 cSt, and ranges in between any two of thesevalues or greater than any one of these values. In some embodiments, theoligomerized product has a kinematic viscosity greater than about 20 cStat 40° C.

Acids for olefin oligomerization include, but are not limited to, Lewisacids such as boron trifluoride and aluminum trichloride. Heterogeneouscatalysts such as zeolites are another class of catalysts for olefinoligomerization. The reactions are conducted in a continuous stirredtank reactor using between about 1 wt % and about 15 wt % of the Lewisacid catalyst based on a oligomerization reactor hydrocarbon feed basis.The Lewis acid catalyst may be at about 2 wt %, about 3 wt %, about 4 wt%, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %,about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt%, and ranges between any two of these values. In some embodiments, theLewis acid catalyst is from about 2 wt % to about 8 wt %. The reactoroperates at a temperature in about the 0° C. to 200° C. range, underabout 1 bar to about 10 bar pressure. The reactor may operate at atemperature of about 10° C., about 20° C., about 30° C., about 40° C.,about 50° C., about 60° C., about 70° C., about 80° C., about 90° C.,about 100° C., about 110° C., about 120° C., about 130° C., about 140°C., about 150° C., about 160° C., about 170° C., about 180° C., about190° C., and ranges in between any two of these values. In someembodiments, the temperature is from about 20° C. to about 120° C. Thereactor may operate at a pressure of about 2 bar, about 3 bar, about 4bar, about 5 bar, about 6 bar, about 7 bar, about 8 bar, about 9 bar,and ranges in between any two of these values or above any one of thesevalues. Reactor residence times are in the range of about 20 minutes toabout 120 minutes. The reactor residence time may be about 30 minutes,about 40 minutes, about 50 minutes, about 60 minutes, about 70 minutes,about 80 minutes, about 90 minutes, about 100 minutes, about 110minutes, and ranges in between any two of these values. In someembodiments, the reactor residence time is from about 30 minutes toabout 90 minutes. The reactor effluent includes products of theoligomerization reaction. Unreacted hydrocarbons, if present, may beseparated from the oligomerized product. The oligomerization product ispredominately dimers and tetramers of the linear internal olefins. Insome embodiments, the dimers and tetramers are greater than 60 wt % ofthe oligomerized product. The oligomerization product of this embodimentincludes long-chain branched hydrocarbons. The unreacted linearhydrocarbons include the paraffin feed to the dehydrogenation reactorand the olefinic fluid not reacted under acid-catalyzed oligomerizationconditions.

The oligomerized product may include a dimer, trimer, tetramer, or amixture of any two or more thereof. The oligomerized product of thepresent technology may contain aromatics in the amount of about 0.9 wt%, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and rangesbetween any two of these values or below any one of these values. Insome embodiments, the oligomerized product contains less than 0.1 wt %total aromatics. In some embodiments, the oligomerized product is freeof benzene. The oligomerized product has a biodegradability of at leastabout 40% after about 23 days of exposure to microorganisms. Thebiodegradability may be about 42%, about 44%, about 46%, about 48%,about 50%, about 52%, about 54%, about 56%, about 58%, about 60%, about62%, about 64%, about 66%, about 68%, about 70%, about 72%, about 74%,about 76%, about 78%, about 80%, and ranges between any two of thesevalues or greater than any one of these values. In some embodiments, theoligomerized product is used as a drilling fluid, a hydraulic fracturingfluid, a metal working fluid, a protecting agent, or a combination ofany two or more thereof.

Peroxide-Initiated Oligomerization:

Organic peroxide treatment may be used to initiate oligomerization ofHDO and/or hydroisomerized HDO products. As stated above, it is to beunderstood that the term “oligomerization” as used herein refers to theformation of a compound from 2, 3, 4, 5, 6, 7, 8, 9 or 10 monomers,where the compound formed by oligomerization is an “oligomer.” Forexample, a dimer is a compound made from the oligomerization of 2monomers, a trimer is a compound made from the oligomerization of 3monomers, and a tetramer is a compound made from the oligomerization of4 monomers. The product composition, comprising dimers and co-dimers ofthe linear and/or branched paraffins, has a kinematic viscosity greaterthan about 10 cSt at 40 C. The product is thus well suited for use invarious mineral oil and lubricating oil applications.

Organic peroxides generate free radicals that extract hydrogen atomsfrom secondary and tertiary carbons of the paraffinic hydrocarbons,providing free radical sites therein for subsequent coupling reactions.The organic peroxides for the reaction are of the formula R—O—O—R′ whereR and R′ are each independently H, alkyl, or aryl. In some embodiments,organic peroxides for the reaction include dialkyl peroxides including,but not limited to, di-tert butyl peroxide (DTBP), 2,5-dimethyl2,5-di(t-butylperoxy)hexane, dicumyl peroxide, dibenzoyl peroxide,dipropyl peroxide, ethyl propyl peroxide, tert-butyl tert-amyl peroxide,or combinations of any two or more thereof.

Peroxide-initiated oligomerization may be carried out in batch orcontinuous reactors. Preferred batch reactor embodiments are agitatedtanks with provisions for heat transfer/temperature control. Theseinclude jackets, internal coils, or pump-around heat exchange.Continuous flow reactors include those approaching plug-flow behaviorsuch as tubular reactors (including, but not limited to, static mixers)and fixed-bed vessels packed with inert media like ceramic balls. Aswith the batch reactors, these plug-flow reactors may include provisionsfor heat transfer/temperature control. A low capital cost embodiment ofthe continuous reactor for peroxide-initiated oligomerization is thejacketed pipe or the pipe-in-pipe reactor.

The reactor feed comprising HDO and/or hydroisomerized HDO paraffinsincludes between about 2 wt % and about 40 wt % organic peroxide and thereactor is controlled at a temperature from about 50° C. to about 250°C. The organic peroxide may be in the amount of about 3 wt %, about 4 wt%, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %,about 10 wt %, about 12 wt %, about 14 wt %, about 16 wt %, about 18 wt%, about 20 wt %, about 22 wt %, about 24 wt %, about 26 wt %, about 28wt %, about 30 wt %, about 32 wt %, about 34 wt %, about 36 wt %, about38 wt %, and ranges between any two of these values or above any one ofthese values. In some embodiments, the organic peroxide is in the amountof about 5 wt % to about 20 wt %. The reactor temperature may be about60° C., about 70° C., about 80° C., about 90° C., about 100° C., about110° C., about 120° C., about 130° C., about 140° C., about 150° C.,about 160° C., about 170° C., about 180° C., about 190° C., about 200°C., about 210° C., about 220° C., about 230° C., about 240° C., andranges in between any two of these values. In some embodiments, thetemperature is between about 70° C. and about 200° C. The reactor iscontrolled at a suitable pressure, high enough to ensure reactorcontents are in liquid phase. This pressure is typically from about 1bar to about 10 bar. The reactor may operate at a pressure of about 2bar, about 3 bar, about 4 bar, about 5 bar, about 6 bar, about 7 bar,about 8 bar, about 9 bar, and ranges in between any two of these valuesor above any one of these values. Batch cycle times, or residence timesof continuous flow reactors, are in the range from about 10 minutes toabout 120 minutes. The reactor residence time may be about 10 minutes,about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes,about 60 minutes, about 70 minutes, about 80 minutes, about 90 minutes,about 100 minutes, about 110 minutes, and ranges in between any two ofthese values. In some embodiments, the reactor residence time is fromabout 20 minutes to about 90 minutes.

In the batch mode, all the peroxide may be charged at once followingaddition of the paraffinic feedstock. The peroxide may also beintroduced in increments over the batch cycle time. In other embodimentsof peroxide-initiated oligomerization, the organic peroxide is fed tothe batch reactor continuously during all or a portion of the batchreaction cycle time, preferably using a metering pump or control valve.This mode of operation is also referred to as “semi-batch” in the art.

The reactor effluent comprises oligomerization products, mainly dimersand trimers of the HDO and/or hydroisomerization paraffins. Theunreacted paraffins, making up between about 0 wt % and about 60 wt % ofthe effluent composition, are optionally stripped (preferably viaatmospheric or vacuum distillation) to yield a oligomerized fluidproduct having a kinematic viscosity greater than about 10 cSt at 40° C.The oligomerized product may have a kinematic viscosity at 40° C. ofabout 12 cSt, about 14 cSt, about 16 cSt, about 18 cSt, about 20 cSt,about 22 cSt, about 24 cSt, about 26 cSt, about 28 cSt, about 30 cSt,and ranges in between any two of these values or greater than any one ofthese values. In some embodiments, the oligomerized product has akinematic viscosity greater than about 20 cSt at 40° C. This product iswell-suited for use in various lubricating applications where acombination of high thermal stability, low ecotoxicity, and good lowtemperature properties is desired. The unreacted paraffins in theeffluent composition may be about 1 wt %, about 2 wt %, 3 wt %, about 4wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt%, about 10 wt %, about 12 wt %, about 14 wt %, about 16 wt %, about 18wt %, about 20 wt %, about 22 wt %, about 24 wt %, about 26 wt %, about28 wt %, about 30 wt %, about 32 wt %, about 34 wt %, about 36 wt %,about 38 wt %, about 40 wt %, about 50 wt % and ranges between any twoof these values or above any one of these values.

The oligomerized product may include a dimer, trimer, tetramer, or amixture of any two or more thereof. The oligomerized product has abiodegradability of at least about 40% after about 23 days of exposureto microorganisms. The biodegradability may be about 42%, about 44%,about 46%, about 48%, about 50%, about 52%, about 54%, about 56%, about58%, about 60%, about 62%, about 64%, about 66%, about 68%, about 70%,about 72%, about 74%, about 76%, about 78%, about 80%, and rangesbetween any two of these values or greater than any one of these values.The oligomerized product of the present technology may contain aromaticsin the amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt%, about 0.1 wt %, and ranges between any two of these values or belowany one of these values. In some embodiments, the oligomerized productcontains less than 0.1 wt % total aromatics. In some embodiments, theoligomerized product is free of benzene. In some embodiments, theoligomerized product is used as a drilling fluid, a hydraulic fracturingfluid, a metal working fluid, a protecting agent, or a combination ofany two or more thereof.

In another aspect, a method is provided involving protecting a substanceby applying the above-described paraffinic fluids. In the method, theparaffinic fluid includes a hydrodeoxygenated product; where thehydrodeoxygenated product is produced by hydrodeoxygenating abio-derived feed; the bio-derived feed comprises bio-derived fattyacids, fatty acid esters, or a combination thereof; thehydrodeoxygenated product comprises n-paraffins; the paraffinic fluidcontains less than 1 wt % aromatics; and the n-paraffins have akinematic viscosity of less than about 10 cSt at 40° C. and have abiodegradability of at least 40% after about 23 days of exposure tomicroorganisms. In some embodiments, the hydrodeoxygenated productincludes n-paraffins in the range of about 80 wt % to about 100 wt %;cycloparaffins in the range of about 0 wt % to about 10 wt %; less thanabout 1 wt % total aromatics. In some embodiments, the paraffinic fluidfurther includes a hydroisomerized product produced by at leastpartially hydroisomerizing the hydrodeoxygenated product; where thehydroisomerized product comprises isoparaffins where at least about 80wt % of the isoparaffins are mono-methyl branched paraffins; themono-methyl branched paraffins comprise less than about 30 wt % terminalbranched isoparaffins; and the isoparaffins have a kinematic viscosityof less than about 10 cSt at 40° C. and have a biodegradability of atleast about 40% after about 23 days of exposure to microorganisms.

Thus, in some embodiments of the method, the substance is a food crop, ametal, or wood. In some embodiments, protecting involves solvating thesubstance. In such embodiments, the substance includes pesticides,herbicides, paints, inks, or coatings. In some embodiments of themethod, protecting involves cleaning the substance with the paraffinicfluid In such embodiments, the substance comprises fabric, metal, orplastic. In some embodiments of the method, protecting involveslubricating the substance where the substance is metal. Such a method isexemplified by the protecting applications listed for dry cleaningfluids, industrial solvents, crop protection solvents/coating oils,grain de-dusting oils, metal working fluids, industrial cleaning fluids,lubricating base oils, polymerization fluids, transformer oils, cosmeticoils, food preparation oils, and drilling fluids and hydraulicfracturing fluids of the present technology.

Dry Cleaning Fluids:

Bio-based synthetic fluids of this technology may be used as asubstitute for petroleum-based solvents and perchloroethylene for drycleaning of apparel. These fluids comprise hydrocarbons in the C₁₀-C₁₅range. The paraffinic nature of the fluid (specifically itsnon-corrosive, non-polar properties) allows it to be used with manysensitive fabrics. They remove oil and grease effectively, aid inremoving water-soluble dirt when combined with effective detergents, andare virtually odorless. The kinematic viscosities of these fluids areless than 10 cSt at 40° C. For reducing risk of fire, the flash point isgenerally above 38° C. Dry cleaning fluids of this technology includehydrocarbons in the C₁₀-C₁₅ range.

Industrial solvents: Bio-based synthetic fluids of this technology maybe used as solvents for paints, inks, adhesives, and coatings. Thesefluids comprise paraffinic hydrocarbons in the C₅-C₂₀ range. Due tovirtual absence of aromatic hydrocarbons and odors, these fluids meetincreasingly stringent regulatory requirements. The bio-based syntheticfluids are characterized by selective solvency as characterized by ananiline number greater than about 80° C., and a Kauri-Butanol valuegreater than about 19. They are an effective substitute forpetroleum-based solvents, including ISOPAR® and SOLTROL® products.(ISOPAR® and SOLTROL® are trademarks of ExxonMobil Chemical and ChevronPhillips Chemical respectively.) The viscosities of these fluids areless than about 10 cSt at 40° C., with volatility (flash point anddistillation/boiling range) adjusted according to the specificapplication. As such, the lighter hydrocarbons, such as those in theC₅-C₇ range, may be stripped/distilled in order to provide industrialsolvents having higher flash points and thus with a reduced risk offire.

Crop Protection Solvents/Coating Oils:

Bio-based synthetic fluids of this technology may be used asagricultural solvents and spray oils. These fluids include paraffinichydrocarbons in the C₅-C₂₀ range for solvent applications (e.g. fordissolving pesticides and herbicides), and in the C₁₆-C₃₆ range forcoating oil applications. Examples of crop protection solventapplications include dissolving and spraying pesticides. These includeapplications where the solvent is used to extract a natural herbicidefor crop protection. In these cases, selective solvency, as indicated byan aniline number greater than about 80° C., and a Kauri-Butanol valuegreater than about 19, is a key attribute of the paraffinic solvent.

When used as coating oil, the fluid is applied to the plant leavesforming a film that protects the plant from fungi and pests. Because thecoating oil is a non-toxic chemical, as defined by an eco-toxicity whereLC₅₀>3.5 mg/L (as described above), the pests cannot become immune tothe product. The spray oil naturally bio-degrades and evaporates duringthe growth cycle of the plant. And because the bio-based fluids arenaturally free-of sulfur, they do not leave a sulfonic residue.Typically, for coating oil applications, the fluid viscosity is greaterthan about 10 cSt at 40° C.

Grain De-Dusting Oil:

This application is similar to the crop protection coating oil.Bio-based synthetic fluids of the present technology that includehydrocarbons in the C₁₆-C₃₆ range provide the required performance,mitigating dust accumulation when handling grain. For this application,fluid viscosity is greater than about 10 cSt at 40° C.

Metal Working Fluids:

Bio-based synthetic fluids of this technology may be used as metalworking fluids, including metal lubricating and metal rolling fluids.For applications such as aluminum rolling (e.g. for preparing rolls ofaluminum foils) paraffinic hydrocarbons in the C₁₁-C₂₀ range, havingkinematic viscosities less than about 10 cSt at 40° C. and flash pointsabove about 60° C. are most suitable.

For applications involving more severe metal-metal contact wherelubricating properties are desired, chlorinated paraffins fromchlorination of the HDO product as described above, or bio-derivedsynthetic fluids of the present technology having a carbon number in theC₁₆-C₃₆ range and a kinematic viscosity greater than about 10 cSt at 40°C. are desired. These fluids cool and lubricate metal surfaces, reducingfriction and tool wear while removing residual metallic pieces.

Industrial Cleaning Fluids:

Bio-based synthetic fluids of this technology are suitable substitutesfor petroleum kerosene for use as industrial cleaners. Unlike thepetroleum kerosene that can have up to 30% aromatic hydrocarbons, thebio-based synthetic fluids contain virtually no aromatics and aretherefore low in toxicity and odor, and meet stringent regulatoryrequirements for occupational exposure.

Lubricating Base Oils:

Bio-based synthetic fluids of this technology, comprising oligomerizedhydrocarbons, have kinematic viscosities greater than about 10 cSt at40° C., preferably greater than about 20 cSt at 40° C., and viscosityindex values (measure of viscosity stability within operatingtemperature range) suitable for lube base oil applications.

Polymerization Fluids:

Bio-based synthetic fluids of this technology may be used for varioussolution and slurry polymerization processes such as the linear lowdensity polyethylene process. Additionally, these fluids may be used forfoam blowing processes, as an environmentally friendly substitute forchlorinated hydrocarbons. Examples of such foam blowing processesinclude production of foamed polystyrene (e.g. STYROFOAM®) and foamedpolyurethane. Isoparaffinic hydrocarbons (e.g. HDO hydroisomerizationproducts) in the C₅-C₉ range are particularly well-suited for theseapplications.

Transformer Oils:

Bio-based synthetic fluids of this technology are suitable for use astransformer fluids due to their low dielectric constants (from about 2to about 3 at in the range from about 50° C. to about 200° C.) and verylow water solubility. Oligomerized bio-based fluids having carbonnumbers in the C₂₀-C₃₆ range are preferred due to their very high flashpoints.

Cosmetic Oils:

Bio-based synthetic fluids of this technology may be used as ingredientsin baby lotions, cold creams, ointments and cosmetics. The odorless,tasteless, and inherently non-toxic attributes of these fluids make themattractive for these applications. The fluids of this technology in theC₁₆-C₃₆ range having a kinematic viscosity greater than about 10 cSt at40 C are particularly well-suited for use in cosmetics.

Food Preparation Oils:

Bio-Based Synthetic Fluids of this Technology May be Used for foodcontact applications. Due to their properties in preventing waterabsorption, and with their inherent non-toxicity and low odor, thesebio-based synthetic fluids may be used to preserve wooden cuttingboards, salad bowls and other wooden kitchenware/utensils. Rubbing smallamounts of the oils on the wooden kitchenware fills cracks therein andprevents water/food accumulation which can lead to formation of bacteriain addition to degradation of the wooden article.

Drilling Fluids and Hydraulic Fracturing Fluids:

Bio-based synthetic fluids of this technology may be used as base fluidsfor drilling mud applications, including for offshore applications wherea good balance of thermal stability, eco-toxicity and bio-degradabilityis desired.

In an aspect, a method is provided which involves producing an orificein a substrate by at least injecting a paraffinic fluid into thesubstrate, wherein the paraffinic fluid comprises a hydrodeoxygenatedproduct; the hydrodeoxygenated product is produced by hydrodeoxygenatinga bio-derived feed; the bio-derived feed comprising bio-derived fattyacids, fatty acid esters, or a combination thereof; thehydrodeoxygenated product comprises n-paraffins; the paraffinic fluidcontains less than about 1 wt % aromatics; and the n-paraffins have akinematic viscosity of less than about 10 cSt at 40° C. and have abiodegradability of at least about 40% after about 23 days of exposureto microorganisms. The paraffinic fluid may be any one of thecompositions provided by the present technology, including, but notlimited to, the oligermized product, the chlorinated product, theolefinic fluid, the HDO product, the hydroisomerized product, ormixtures of any two or more thereof. As described above, the paraffinicfluids of the present technology have flash points, thermal stabilities,viscosities, eco-toxicities and biodegradabilities excellently suitedfor such a method. In some embodiments, the hydrodeoxygenated productincludes n-paraffins in the range of about 80 wt % to about 100 wt %;cycloparaffins in the range of about 0 wt % to about 10 wt %; and lessthan about 1 wt % total aromatics. In some embodiments, the paraffinicfluid further includes a hydroisomerized product produced by at leastpartially hydroisomerizing the hydrodeoxygenated product; wherein thehydroisomerized product comprises isoparaffins where at least about 80wt % of the isoparaffins are mono-methyl branched paraffins; themono-methyl branched paraffins comprise less than about 30 wt % terminalbranched isoparaffins; and the isoparaffins have a kinematic viscosityof less than about 10 cSt at 40° C. and have a biodegradability of atleast about 40% after about 23 days of exposure to microorganisms.

In some embodiments, the paraffinic fluid has a kinematic viscosity lessthan about 10 cSt at 40° C. In such embodiments, the paraffinic fluidmay have a kinematic viscosity at 40° C. of about 9 cSt, about 8 cSt,about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2cSt, about 1 cSt, and ranges in between any two of these values or belowany one of these values. In some embodiments, the paraffinic fluid has akinematic viscosity greater than about 10 cSt at 40° C. In suchembodiments, the paraffinic fluid may have a kinematic viscosity at 40°C. of about 12 cSt, about 14 cSt, about 16 cSt, about 18 cSt, about 20cSt, about 22 cSt, about 24 cSt, about 26 cSt, about 28 cSt, about 30cSt, and ranges in between any two of these values or greater than anyone of these values. In some embodiments, the paraffinic fluid has akinematic viscosity greater than about 20 cSt at 40° C.

In some embodiments, the substrate comprises a soil substrate, a topsoilsubstrate, a subsoil substrate, a clay substrate, a sand substrate, arock substrate, or a stone substrate. In some embodiments, thebio-derived fatty acids, fatty acid esters, or a combination thereofcomprises algae oils, beef tallow, camelina oil, canola oil, rapeseedoil, castor oil, choice white grease, coconut oil, coffee bean oil, cornoil, cottonseed oil, fish oils, hemp oil, Jatropha oil, linseed oil,mustard oil, palm oil, palm kernel oil, poultry fat, soybean oil,sunflower oil, tall oil, tall oil fatty acid, Tung oil, used cookingoils, yellow grease, products of the food industry, or combinations ofany two or more thereof. In some embodiments, the bio-derived fattyacids, fatty acid esters, or a combination thereof comprise soybean oil,corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil, palmoil, palm kernel oil, rapeseed oil, or a combination of any two or morethereof. In some embodiments, the step of producing an orifice compriseshydraulic fracturing of the substrate with the paraffinic fluid.

Integrated Process for Production of Bio-Based Industrial Fluids:

An embodiment of the inventive method for producing bio-based industrialfluids is presented in FIG. 1. Referring to FIG. 1, a bio-based feed 102comprising fatty acids and/or fatty acid esters is combined with acompressed treat gas 104 to form reactor feed stream 106 and achievehydrodeoxygenation (HDO) in HDO unit 110. The bio-based feed 102comprises any one or more of the oils, fats, or greases recited earlierherein in this application. The bio-based feed 102 and treat gas 104 arepumped and compressed respectively to a pressure within the rangedescribed earlier herein.

The treat gas 104 for the HDO reaction is a hydrogen-rich gas, with ahydrogen concentration in the range of about 70 mol % to about 100 mol%. In some embodiments, the hydrogen concentration is between about 82mol % and about 99 mol %. The main impurities present in the treat gas104 include methane, ethane, propane, n-/iso-butane, hydrogen sulfide,carbon monoxide, carbon dioxide, ammonia, and water.

The HDO unit 110 comprises a preheater to raise the temperature ofreactor feed 106 to achieve HDO reactor operation within the temperaturerange described previously in the application. In addition to thepreheater, the HDO unit 110 includes an HDO reactor, separatordrums/vessels, and a product stripper. The drums/vessels separate awater byproduct 112 and an HDO gas 114 from HDO product 116. The productstripper is employed for removal of residual byproduct ammonia, hydrogensulfide, and carbon oxides, dissolved in the HDO product 116. The HDOproduct 116 is a paraffinic hydrocarbon composition comprisingn-paraffins in the C₁₅-C₁₈ range, with elemental sulfur and elementalnitrogen less than about 5 wppm and elemental oxygen less than about 0.1wt %. In some embodiments, elemental sulfur and elemental nitrogen areless than 1 wppm in the paraffinic hydrocarbon composition. In someembodiments, the HDO product 116 is partially recycled to the HDOreactor as a solvent/diluent for bio-based feed 102.

The HDO gas 114, containing same byproducts in addition to lighthydrocarbons such as methane and propane, is optionally subjected totreatment (e.g. scrubbing with a solvent, water, or caustic/aminesolutions) to reduce the concentration of these molecules in the gas114. In some embodiments, the gas 114 is partially recycled to the HDOreactor.

The HDO product 116 is combined with treat gas 118 to form ahydroisomerization unit feed 119. The treat gas is a hydrogen-rich gasstream having the specifications of treat gas 104, but preferablycontaining less than about 10 ppm hydrogen sulfide, ammonia, or carbonmonoxide. If needed, the HDO product 116 and treat gas 118 arepressurized/compressed to a value within the hydroisomerizationoperating pressure range specified earlier in this application.

The hydroisomerization unit 120 comprises a feed preheater, ahydroisomerization reactor, and separation drums for separating thehydroisomerization product 124 from the hydroisomerization gas 122. Thehydroisomerization gas 122 may contain light hydrocarbons formed in thehydroisomerization reactor via hydrocracking side reactions therein.

The preheater in the hydroisomerization unit 120 raises the temperatureof the feed for operating the hydroisomerization reactor within thetemperature range indicated earlier in this application.

The hydroisomerization gas 122 is combined with the treat gas 104 and/orthe treat gas 118, via a compression stage if desired.

The hydroisomerization product 124, comprising paraffinic hydrocarbonsin the C₅-C₁₈ range, is directed to oligomerization unit 130, where itis combined with an organic peroxide initiator 126 according toconditions and limitations provided previously. In embodiments where abatch oligomerization reactor is employed, the oligomerization unit 130is equipped with a plurality of feed tanks. In these embodiments, onetank is used to charge the oligomerization reactor while the other isbeing filled with hydroisomerization product 124. The oligomerizationeffluent 132 includes both oligomerized and unconverted components ofhydroisomerization product 124. As such, the oligomerization effluent132 is a paraffinic hydrocarbon composition in the C₅-C₃₇+ range,characterized by a high degree of C₂+ chain branching.

The oligomerization effluent is directed to a fractionation unit 140.The fractionation unit may be one distillation column with side draws,or a plurality of columns operating at different pressures. Therein theoligomerization effluent is fractionated into Fraction 142 comprisinghydrocarbons in the C₅-C₁₅ range, Fraction 144 comprising hydrocarbonsin the C₁₆-C₁₈ range, and Fraction 146 comprising hydrocarbons in theC₁₉-C₃₇+ range. Fraction 144 may be used for solvents, drilling fluids,hydraulic fracturing fluids, and other industrial fluid applicationswhere kinematic viscosity values are less than about 10 cSt at 40° C.Fraction 146 may be used for lubricating oils, dielectric fluids, grainde-dusting fluids, mineral oil, and other applications where thekinematic viscosity is greater than about 10 cSt at 40 C. In someembodiments, it is necessary to further fractionate the fluid fractioncomprising C₃₇+ fractions in order to meet the maximum boilingtemperature specified for the fluid.

Fraction 142 may be partially or completely recycled to oligomerizationunit 130. Alternatively, Fraction 142 may be further fractionated into aC₅-C₉ ranged and C₁₀-C₁₅ ranged fractions for use as other solvents orfuels. The fluid fractions are preferably additized with ananti-oxidant, and other additives specific to the application, beforedrumming and shipping. The anti-oxidant is preferably a hindered phenolintroduced at a concentration between about 2 and about 200 wppm. Insome embodiments, the anti-oxidant is at a concentration between about10 wppm and about 100 wppm.

The present invention, thus generally described, will be understood morereadily by reference to the following examples, which are provided byway of illustration and are not intended to be limiting of the presentinvention.

EXAMPLES Example 1 Demonstration of the Bio-Degradability of a Bio-BasedSynthetic Hydrocarbon Fluids

Canola oil was hydrodeoxygenated in a 100 cc tubular reactor packed with20 cc Mo catalyst (top layer) and 80 cc NiMo catalyst (bottom layer) andthen pressurized to 1600 psig with hydrogen. The catalysts werecommercially available products obtained in oxide form. The catalystswere sulfided in the reactor using dimethyl disulfide (DMDS), followinga ramp-hold temperature profile. The first hold was 12 hrs at 400° F.(wherein H₂S breakthrough was confirmed), and the second hold was about10 hrs at 700° F. The temperatures were lowered to about 450° F. beforeintroduction of 100% canola oil (spiked with 100 ppm sulfur as DMDS).After a break-in period of partial hydrodeoxygenation, the reactortemperature was raised to 640 F. The liquid hourly space velocity ofcanola oil was maintained at 1 vol/vol/hr, along with a 10,000 SCF/Bblgas-to-oil ratio.

The canola oil feed and HDO product were both analyzed for elementaloxygen. The feed was 11.1 wt % oxygen whereas the HDO product was belowdetection limit (<0.1 wt % oxygen). The HDO product had a flash point of138° C., a viscosity of 3.68 cSt at 40° C., and density of 0.800 kg/L.

The HDO product was subjected to biodegradability test according to ASTMD5864-05. After 23 days of exposure to microorganisms at the conditionsspecified in the test method, with room temperature in the 20-25° C.range, the paraffinic HDO product degradation as measured by CO₂production was found to be 44.2%. By comparison, the biodegradability ofpoly alpha olefins is reported to be in the 0-25% range.

Example 2 Hydroisomerized HDO Product Fractions

HDO paraffins were hydroisomerized (HI) according to the conditionsdescribed in this technology, using a Pt/Pd-on-amorphous silica/aluminacatalyst. The hydroisomerized products were fractionated into differentcuts using both laboratory as well as commercial scale distillationcolumns. The fractionation cuts' boiling ranges corresponded tocommercial grades of petroleum-based paraffinic fluids such as ISOPAR®L, ISOPAR® M, ISOPAR® V, SOLTROL® 170, and SOLTROL® 220. The results aresummarized in Table 1.

TABLE 1 Comparison of Bio-Based Isoparaffin Fluid Fractions (HI Cuts) toCommercial Retro-Solvents ISOPAR GRADE L M V ISOPAR and EquivalentProducts ISOPAR HI Cut 2 ISOPAR SOL-170 HI Cut 3 ISOPAR SOL-220 HI Cut 4HI BTMS Solvency Kauri-butanol value, ASTM D1133 27 25 25 24.6 23 23 NA³ 20.5 19 Aniline Point (° C.) 85 80 91 91 86 92 NA 94 98 VolatilityFlash Point, ASTM D56 (° C.) 64 60 93 87 87 129 100 121 124Distillation, ASTM D86 IBP (° C.) 189 165 223 ≧216 198 273 ≧218 228 273Distillation, ASTM D86 EP (° C.) 207 209 254 ≦246 243 312 ≦315 281 304Specific Gravity @ 15.6 C, 0.77 0.77 0.79 0.78 0.77 0.83 NA 0.78 0.784ASTM D1250 Composition, wt % Saturates 99.9 >99 99.9 >99 99.8 NA >9999.7 Aromatics <0.01 <1 <0.05 0.01 <1 <0.5 NA <1 0.3 Notes: 1. ISOPAR isa trademark of ExxonMobil Chemical 2. SOLTROL (“SOL”) is a trademark ofChevron Phillips Chemical ³NA = Data not available

As observed in Table 1, the bio-based fluids, HI Cuts 2-4 and HI Btms,have the desired selective solvency for use as industrial solvents:Kauri-Butanol values greater than about 19, and aniline points greaterthan about 80° C.

The HI Btms fraction was further analyzed for comparison with twocommercial petroleum-based drilling fluids, recognized for theirrelatively low ecotoxicity, high flash points, and low pour points.These products are offered for offshore applications. Table 2 provides asummary of the results.

TABLE 2 Comparison of Bio-Based Isoparaffinic Fluid (HI Btms) toCommercial Petro-Based Drilling Fluids CLAIRSOL ESCAID HI Property NS^((a)) 120 ^((b)) Btms Specific Gravity 0.82 0.818 0.784 Flash Point, °C. 122 101 124 Pour Point, ° C. −18 −24 <−12 Aromatics, wt % <0.5 0.9<0.5 Viscosity at 20° C., cSt Viscosity at 40° C., cSt 3.4 2.36 3.49Aniline Pt., ° C. 84 98 Distillation, ° C. IBP 261 235 273 FBP 293 270304 Notes: ^((a)) CLAIRSOL is tradename of Petrochem Carless, a leadingsupplier of drilling base fluids in Europe ^((b)) ESCAID is tradename ofExxonMobil Chemical, a leading supplier of drilling base fluids

The table shows that the bio-based drilling fluid (or drilling mud basefluid) meets all the performance parameters presently provided by thepetroleum-based drilling fluids.

Example 3 Peroxide-Initiated Oligomerization of Paraffins

100 parts by weight of a hydroisomerized HDO product is introduced to around-bottom flask reactor equipped with a mechanical stirrer, a refluxcondenser, a temperature indicator, and a heating mantle. Thehydroisomerized HDO product is analyzed via gas chromatography (GC) andis found to consist mainly of C₉-C₁₈ n-paraffins and iso-paraffins. Uponreaching about 200° C., 20 parts by weight of LUPEROX 101 organicperoxide [2,5-dimethyl 2,5-di(t-butylperoxy)hexane; purchasable fromAldrich] is added in 10 equal parts over 5 hours. Upon reaching the6^(th) hour, the reactor is cooled and analyzed via GC where increase incarbon number is confirmed. The product is distilled to remove thelighter, un-reacted components and the byproducts of peroxidedecomposition. The higher carbon number product is then tested forbiodegradability according to D5864 guidelines and expected to displayat least 40+% biodegradation after 23 days of exposure tomicro-organisms.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations can be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

Other embodiments are set forth in the following claims.

What is claimed is:
 1. A method comprising altering the viscosity ofbio-derived paraffins to produce a paraffinic fluid, wherein thealtering step comprises oligomerizing the bio-derived paraffins toproduce an oligomerized product, wherein the oligomerized product has akinematic viscosity of at least about 10 cSt at 40° C.; the paraffinicfluid comprises the oligomerized product; the bio-derived paraffinscomprise a hydrodeoxygenated product produced by hydrodeoxygenating abio-based feed where the bio-based feed comprises bio-derived fattyacids, fatty acid esters, or a combination thereof; and the bio-derivedparaffins comprise n-paraffins where the n-paraffins have a kinematicviscosity of less than about 10 cSt at 40° C.; and have abiodegradability of at least about 40% after about 23 days of exposureto microorganisms.
 2. The method of claim 1, wherein the oligomerizedproduct comprises less than about 1 wt % aromatics.
 3. The method ofclaim 1, wherein the oligomerized product comprises less than about 0.1wt % aromatics.
 4. The method of claim 1, wherein the oligomerizedproduct is free of benzene.
 5. The method of claim 1, wherein thealtering step comprises oligomerizing bio-derived paraffins within theC₁₆-C₁₈ range.
 6. The method of claim 1, wherein oligomerizingbio-derived paraffins comprises contacting the bio-derived paraffinswith an organic peroxide to produce the oligomerized product.
 7. Themethod of claim 6, wherein the oligomerized product has abiodegradability of at least about 40% after about 23 days of exposureto microorganisms.
 8. The method of claim 6, wherein the oligomerizedproduct is a dimer, trimer, tetramer, or a mixture of any two or morethereof.
 9. The method of claim 6, wherein the organic peroxide ispresent in an amount between about 2 wt % and about 40 wt % based on thetotal weight of the bio-derived paraffins and the organic peroxide. 10.The method of claim 6, wherein the organic peroxide is of the formulaR—O—O—R′ where R and R′ are each independently H, alkyl, or aryl. 11.The method of claim 6, wherein the organic peroxide comprises di-tertbutyl peroxide, 2,5-dimethyl 2,5-di(t-butylperoxy)hexane, dicumylperoxide, dibenzoyl peroxide, dipropyl peroxide, ethyl propyl peroxide,or tert-butyl tert-amyl peroxide.
 12. The method of claim 6, wherein thecontacting is performed at a temperature between about 50° C. and about250° C.
 13. The method of claim 6, wherein the organic peroxide ispresent in an amount between about 5 wt % and about 20 wt % based on thetotal weight of the bio-derived paraffins and the organic peroxide; andthe contacting is performed at a temperature between about 60° C. andabout 200° C.
 14. The method of claim 6, wherein the oligomerizedproduct is used as a drilling fluid, a hydraulic fracturing fluid, ametal working fluid, a protecting agent, or a combination of any two ormore thereof.
 15. The method of claim 1, wherein the bio-derivedparaffins are produced by hydrodeoxygenating the bio-based feed toproduce a hydrodeoxygenated product; and at least partiallyhydroisomerizing the hydrodeoxygenated product to produce ahydroisomerized product; wherein the bio-derived paraffins comprise thehydrodeoxygenated product and the hydroisomerized product; thehydrodeoxygenated product comprises n-paraffins; the hydroisomerizedproduct comprises isoparaffins where at least about 80 wt % of theisoparaffins are mono-methyl branched paraffins; the mono-methylbranched paraffins comprise less than about 30 wt % terminal branchedisoparaffins; and the isoparaffins have a kinematic viscosity of lessthan about 10 cSt at 40° C.; and have a biodegradability of at leastabout 40% after about 23 days of exposure to microorganisms.
 16. Themethod of claim 15, wherein the hydrodeoxygenated product comprisesn-paraffins in the range of about 80 wt % to about 100 wt %;cycloparaffins in the range of about 0 wt % to about 10 wt %; and lessthan about 1 wt % total aromatics.
 17. The method of claim 1, whereinthe bio-derived fatty acids, fatty acid esters, or a combination thereofcomprises algae oils, beef tallow, camelina oil, canola oil, rapeseedoil, castor oil, choice white grease, coconut oil, coffee bean oil, cornoil, cottonseed oil, fish oils, hemp oil, Jatropha oil, linseed oil,mustard oil, palm oil, palm kernel oil, poultry fat, soybean oil,sunflower oil, tall oil, tall oil fatty acid, Tung oil, used cookingoils, yellow grease, products of the food industry, or combinations ofany two or more thereof.
 18. The method of claim 1, wherein thebio-derived fatty acids, fatty acid esters, or a combination thereofcomprise soybean oil, corn oil, cottonseed oil, canola oil, coconut oil,sunflower oil, palm oil, palm kernel oil, rapeseed oil, or a combinationof any two or more thereof.